Tracking the energy flow along the reaction path
Shannon Yan, Yen-Tien Wu, Kopin Liu*
Proceedings of the National Academy of Sciences of the United States of America, 105, 12667 -12672 (2008)
Wereport a comprehensive study of the quantum-state correlation property of product pairs from reactions of chlorine atoms with both the ground-state and the CH stretch-excited CHD3. In light of
available ab initio theoretical results, this set of experimental data provides a conceptual framework to visualize the energy-flow pattern along the reaction path, to classify the activity of different vibrational modes in a reactive encounter, to gain deeper insight
into the concept of vibrational adiabaticity, and to elucidate the intermode coupling in the transition-state region. This exploratory approach not only opens up an avenue to understand polyatomic reaction dynamics, even for motions at the molecular level in the fleeting transition-state region, but it also leads to a generalization of Polanyi’s rules to reactions involving a polyatomic molecule.